Crosslinkable polymers of unsaturated imides

ABSTRACT

New crosslinkable polymers, in particular polymerization products of 5-maleimidyl-trimellitic acid derivatives and 3,5-bis-(maleimidyl)-phthalic acid derivatives and vinyl monomers and polycondensation products of the said imidyl compounds and diamines, diols or amino-alcohols and optionally a di-, tri- or tetra-carboxylic acid derivative are described. These polymers are distinguished by good processability and good solubility in customary organic solvents and are suitable for the manufacture of very diverse industrial products, such as thin and thick films and the like.

This is a divisional of application Ser. No. 696,350, filed on June 15,1976, now U.S. Pat. No. 4,115,359, issued on Sept. 19, 1978.

The present invention relates to new crosslinkable polymers and theiruse for the manufacture of crosslinked polymers.

The new crosslinkable polymers, and the corresponding cyclisedderivatives, have an average molecular weight of at least 1,200 and aremanufactured by

(a) polymerising 0.5 to 100 mol % of a compound of the formula Ia or IIa##STR1## with 0 to 99.5 mol % of a compound of the formula III ##STR2##or

(b) reacting 0.5 to 100 mol % of a compound of the formula Ib or IIb##STR3## and 0 to 99.5 mol % of a compound of the formula IV ##STR4##with substantially stoichiometric amounts of a compound of the formula V

    HY--Q--XH                                                  (V)

in which formulae m and n independently of one another represent thenumber 1 or 2, A represents a radical of the formula ##STR5## R₂represents a hydroxyl group, an unsubstituted or substituted phenoxygroup, an alkoxy group with 1-18 carbon atoms or a --O⁻ M⁺ group, or thetwo R₂ s conjointly represent the --O-- grouping, R₂ ' represents anunsubstituted or substituted phenoxy group or an alkoxy group with 1-18carbon atoms, or the two R₂ 's conjointly represent the --O-- grouping,and, when R₂ represents an unsubstituted or substituted phenoxy group oran alkoxy group with 1-18 carbon atoms, or the two R₂ s conjointlyrepresent --O--, R₁ represents a hydroxyl group, an unsubstituted orsubstituted phenoxy group, an alkoxy group with 1-18 carbon atoms or a--O⁻ M⁺ group and, when R₂ represents a hydroxyl group, R₁ represents ahydroxyl group, an unsubstituted or substituted phenoxy group or analkoxy group with 1-18 carbon atoms and, when R₂ represents a --O⁻ M⁺group, R₁ represents a --O⁻ M⁺ group, an unsubstituted or substitutedphenoxy group or an alkoxy group with 1-18 carbon atoms, R₁ ' representsa chlorine atom, an unsubstituted or substituted phenoxy group or analkoxy group with 1-18 carbon atoms, M⁺ represents an alkali metalcation, a trialkylammonium cation with 3-24, and especially 3-12, carbonatoms or a quaternary ammonium cation, R₃ and R₄ independently of oneanother represent hydrogen, chlorine or bromine, X and Y independentlyof one another represent ##STR6## hydrogen, alkyl with 1-4 carbon atomsor phenyl, Q represents an aliphatic radical with at least 2 carbonatoms or a cycloaliphatic, araliphatic, carbocyclic-aromatic orheterocyclic-aromatic radical, or --Y--Q--X represents the grouping##STR7## R₆ and R₇ independently of one another represent hydrogen,methyl or phenyl and Q₁ represents an aliphatic radical or acycloaliphatic, carbocyclic-aromatic or heterocyclic-aromatic radical,in which the carbonyl and carboxyl groups are bonded to different carbonatoms and the carboxyl groups are each in the ortho-position relative toa carbonyl group, Z₁ and Z₃ each represent hydrogen, Z₂ representshydrogen, chlorine or methyl and Z₄ represents hydrogen, methyl, ethyl,chlorine, --CN, --COOH, --CONH₂, phenyl, methylphenyl, methoxyphenyl,cyclohexyl, pyridyl, imidazolyl, pyrrolidonyl, --COO--alkyl with 1-12carbon atoms in the alkyl part, --COO--phenyl, ##STR8## --COO--alkyl--OHwith 1-3 carbon atoms in the alkyl part or ##STR9## wherein R₈ denotes alinear or branched saturated aliphatic radical with at most 10 carbonatoms, R₉ denotes hydrogen or methyl and x denotes an integer from 1 to3; --OCO--alkyl with 1-4 carbon atoms in the alkyl part, --OCO--phenyl,--CO--alkyl with 1-3 carbon atoms in the alkyl part, alkoxy with 1-6carbon atoms, phenoxy, --CH═CH₂ or ##STR10## or Z₁ and Z₂ each representhydrogen and Z₃ and Z₄ conjointly form the ##STR11## grouping and M₁represents a chlorine atom, a hydroxyl group, an unsubstituted orsubstituted phenoxy group or an alkoxy group with 1-18 carbon atoms or,when m and/or n=2, M₁, conjointly with M₂, forms the --O-- grouping andthe groups --COM₁ and --COM₂ are bonded to different carbon atoms andthe --COM₁ groups are each in the ortho-position relative to a --COM₂group, and the resulting polymers are optionally subsequently cyclised.

Polymers according to the invention which are manufactured bypolymerisation of a compound of the formula Ia or IIa with a compound ofthe formula III and have an average molecular weight of about 10,000 to700,000, but especially polymers which are manufactured by acondensation reaction of a compound of the formula Ib or IIb and acompound of the formula IV with a compound of the formula V and have anaverage molecular weight of about 1,500 to 70,000, are preferred.

According to a further preference, 1-50 mol % of a compound of theformula Ia or IIa and 50-99 mol % of a compound of the formula III, or3-50 mol % of a compound of the formula Ib or IIb and 50-97 mol % of acompound of the formula V are used.

A preferably represents a group of the formula ##STR12## but especiallya --CH═CH-- group.

If R₁, R₁ ', R₂, R₂ ' or M₁ represent substituted phenoxy groups, thelatter are, in particular, phenoxy groups which are substituted by nitrogroups or alkyl or alkoxy groups with 1 or 2 carbon atoms or by halogenatoms, above all chlorine or fluorine, such as the 2-, 3- or4-nitrophenoxy group, the 2,4- or 3,5-dinitrophenoxy group, the3,5-dichlorophenoxy group, the pentachlorophenoxy group or the 2-methyl-or 2-methoxy-phenoxy group.

Alkoxy groups R₁, R₁ ', R₂, R₂ ' and M₁ can be straight-chain orbranched. Examples which may be mentioned are: the methoxy, ethoxy,n-propoxy, isopropoxy, n-butoxy, tert.-butoxy, hexyloxy, octoxy,decyloxy, dodecyloxy, tetradecyloxy and octadecyloxy group.Unsubstituted phenoxy groups or alkoxy groups with 1-12, and especially1-4, carbon atoms are preferred.

If R₁ or R₂ denotes a --O⁻ M⁺ group, M⁺ represents, for example, thelithium, sodium, potassium, trimethylammonium, triethylammonium,methyl-diethylammonium, tri-n-octylammonium, benzyltrimethylammonium ortetramethylammonium cation. M⁺ preferably represents the sodium cation.

X and Y preferably have the same meaning.

If R₅ represents an alkyl radical, this contains, in particular, 1 or 2carbon atoms. However, R₅ preferably denotes hydrogen.

R₆ and R₇ preferably have the same meaning and represent, in particular,hydrogen or methyl.

The polymers according to the invention are so-called statisticalcopolymers and polycondensation products which have a statisticaldistribution of the various structural elements.

In the formulae IV and V, the individual Q and Q₁ can have differentmeanings.

Aliphatic, araliphatic, cycloaliphatic, carbocyclic-aromatic orheterocyclic-aromatic radicals represented by Q can be unsubstituted orsubstituted, for example by halogen atoms, such as fluorine, chlorine orbromine, or by alkyl or alkoxy groups each with 1 to 4 carbon atoms.

Possible aliphatic radicals Q are, above all, straight-chain or branchedalkylene groups with 2 to 12 carbon atoms and it is also possible forthe alkylene chain to be interrupted by hetero-atoms, such as O, S or Natoms.

In the meaning of a cycloaliphatic radical, Q represents, for example,the 1,3- or 1,4-cyclohexylene, 1,4-bis(methylene)-cyclohexane ordicyclohexylmethane group, whilst possible araliphatic radicals are,above all, 1,3-, 1,4- or 2,4-bis-alkylenebenzene groups,4,4'-bis-alkylene-diphenyl groups and 4,4'-bis-alkylene-diphenyl ethergroups.

If Q represents a carbocyclic-aromatic radical, such radicals arepreferably monocyclic, condensed polycyclic or non-condensed bicyclicaromatic radicals and in the case of the latter the aromatic nuclei arebonded to one another by means of a bridge member.

Examples of suitable bridge members which may be mentioned are:##STR13## wherein Q₂ denotes an alkyl group with 1-6, and preferably1-4, carbon atoms or a phenyl group.

Non-condensed bicyclic aromatic radicals Q can also be bonded to oneanother via two bridge members, such as two --SO₂ -- groups.

If Q denotes a heterocyclic-aromatic radical, such radicals are, inparticular, heterocyclic-aromatic 5-membered or 6-membered ringscontaining O, N and/or S.

If Q₁ represents an aliphatic radical, such radicals are, preferably,unsubstituted, straight-chain or branched saturated alkylene radicalswith 1 to 10, and especially 2 to 10, carbon atoms.

Cycloaliphatic radicals represented by Q₁ are, above all, 5-membered or6-membered cycloalkylene groups.

If Q₁ denotes a carbocyclic-aromatic radical, this preferably containsat least one 6-membered ring; in particular, such radicals aremonocyclic radicals, condensed polycyclic radicals or polycyclicradicals which have several cyclic, condensed or non-condensed systems,which can be bonded to one another direct or via bridge members.Possible bridge members are the groups mentioned in the foregoing textwhen Q was discussed.

If Q₁ represents a heterocyclic-aromatic radical, possible radicals are,in particular, 5-membered or 6-membered heterocyclic-aromatic,optionally benzo-condensed, ring systems containing O, N and/or S.

Carbocyclic-aromatic or heterocyclic-aromatic radicals represented by Q₁can also be substituted, for example by nitro groups, alkyl groups with1 to 4 carbon atoms, trifluoromethyl groups, halogen atoms, especiallychlorine, or silyl, sulphonic acid or sulphamoyl groups.

Preferably, the individual Q's independently of one another represent anunsubstituted alkylene group with 2 to 10 carbon atoms, abis-(methylene)-cyclohexane group, an unsubstituted monocyclicaraliphatic radical or a monocyclic or non-condensed bicyclic aromaticradical which is optionally substituted by halogen atoms or alkyl oralkoxy groups, each with 1 to 4 carbon atoms, whilst the individual Q₁ sindependently of one another denote an unsubstituted alkylene group with4 to 10 carbon atoms or an unsubstituted monocyclic, condensed bicyclicor non-condensed bicyclic aromatic radical and, in the case of thelatter, the aromatic nuclei are bonded to one another by means of thebridge member --O--, --CO-- or --SO₂ --.

Polymers which are manufactured by polymerisation of 1-50 mol % of acompound of the formula Ia, wherein A represents the group --CH═CH--, R₁represents --OH or an alkoxy group with 1-4 carbon atoms and the two R₂s conjointly represent the --O-- grouping, with 50-99 mol % of acompound of the formula III, wherein Z₁ and Z₃ each denote hydrogen, Z₂denotes hydrogen or methyl and Z₄ denotes --COO--alkyl with 1-10 carbonatoms in the alkyl part, or wherein Z₁, Z₂ and Z₃ each denote hydrogenand Z₄ denotes --CN, chlorine, phenyl or --OCOCH₃, and polymers whichare manufactured by reacting 3-50 mol % of a compound of the formula Iband 50-97 mol % of at least one compound of the formula IV with acompound of the formula V, and in some cases subsequently cyclising thereaction product, in which formulae A represents the group --CH═CH--, R₁' represents a chlorine atom or an alkoxy group with 1-4 carbon atomsand the two R₂ 's conjointly represent the --O-- grouping and n, m, M₁,M₂, X, Y, Q and Q₁ have the following meanings: X and Y each denote--NH--, Q denotes the 1,3- or 1,4-phenylene group, the4,4'-diphenylmethane radical or the 4,4'-diphenyl ether radical or anunsubstituted alkylene group with 2-12 carbon atoms and, when m and n=1,the M₁ s each denote a chlorine atom and Q₁ denotes the 1,3-or1,4-phenylene group and, when m=1 and n=2, one M₁ denotes a chlorineatom and the other, conjointly with M₂ denotes the --O-- grouping and Q₁denotes a benzene ring and, when m and n=2, one M₁ and one M₂ conjointlydenote the --O-- grouping and Q₁ denotes a benzene ring or thebenzophenone ring system; one of X and Y denotes --O-- and the otherdenotes --NH--, Q denotes the 1,3- or 1,4-phenylene group, m and ndenote the number 1, the M₁ s each denote a chlorine atom and Q₁ denotesthe 1,3- or 1,4-phenylene group, or X and Y each denote --O--, Q denotesan unsubstituted alkylene group with 2-12 carbon atoms, m and n denotethe number 1, the M₁ s each denote a chlorine atom and Q₁ denotes a 1,3-or 1,4-phenylene group, are particularly preferred.

The starting compounds of the formulae Ia, Ib, IIa and IIb can beobtained when an amine of the formula VIa or VIb ##STR14## is reactedwith an anhydride of the formula VII ##STR15## and the resultingamide-carboxylic acid of the formula VIIIa or VIIIb ##STR16## issubsequently cyclised and the reaction product is optionally convertedinto another derivative, according to the definition, of the formula Ia,Ib, IIa or IIb.

In the above formulae R₂ " denotes a hydroxyl group, an unsubstitutedphenoxy group or a substituted phenoxy group which is free fromelectronegative substituents, an alkoxy group with 1-18 carbon atoms ora --O⁻ M⁺ group and, when R₂ " represents a phenoxy or alkoxy groupaccording to the definition, R₁ " denotes a hydroxyl group, anunsubstituted phenoxy group or a substituted phenoxy group which is freefrom electronegative substituents, an alkoxy group with 1-18 carbonatoms or a --O⁻ M⁺ group and, when R₂ " represents a hydroxyl group, R₁" also denotes a hydroxyl group or denotes a phenoxy or alkoxy groupaccording to the definition and, when R₂ " represents a --O⁻ M⁺ group,R₁ " also denotes a --O⁻ M⁺ group or denotes a phenoxy or alkoxy groupaccording to the definition and A and M⁺ have the meaning indicatedunder the formulae Ia, IIa, Ib and IIb.

The reaction of the amines of the formula VIa or VIb with the anhydrideof the formula VII can be carried out in the melt or in an aqueous,aqueous-organic or, preferably, an organic medium.

Customary catalysts, such as sodium acetate or triethylamine, and/ordehydrating agents, for example acetic anhydride, can be used forcyclisation of the amide-carboxylic acids of the formula VIIIa or VIIIb.Under certain circumstances, that is to say depending on the nature ofthe substituent R₂ ", for example when R₂ "═OH or --O⁻ M⁺, formation ofthe anhydride also takes place simultaneously with the formation of theimide.

However, the cyclisation (formation of the imide and, in some cases, theanhydride) can also be carried out by the action of heat, by heating totemperatures of about 40°-150° C.

The conversion of the resulting compounds into other derivativesaccording to the definition can be carried out in a manner which is initself known. Acid chlorides of the formula Ib can be manufactured, forexample, by reacting compounds of the formula Ia wherein R₁ "═--OH or--O⁻ M⁺ with suitable chlorinating agents, such as thionyl chloride.

Compounds of the formulae Ia, Ib, IIa and IIb wherein R₁, R₁ ', R₂and/or R₂ ' denote phenoxy groups which contain electronegativesubstituents, such as a nitro group or halogen atoms, are appropriatelymanufactured by reacting corresponding compounds in which R₁, R₁ ', R₂and/or R₂ '═OH with suitable alcohols, or by trans-esterification.

Finally, it is also possible to convert compounds of the formulae Ia,Ib, IIa and IIb wherein A represents --CH═CH-- into compounds of theformulae Ia, Ib, IIa and IIb wherein A denotes the group ##STR17## by anaddition reaction with 1,3-butadiene, cyclopentadiene or furane.

The compounds of the formulae III to V which can be employed in theprocess according to the invention are known or can be manufacturedaccording to methods which are in themselves known. Examples which maybe mentioned are:

COMPOUNDS OF THE FORMULA III

Ethylene, propylene, 1-butene, isoprene, 1,4-butadiene, vinyl chloride,vinylidene chloride, acrylic acid, methacrylic acid, acrylonitrile,methacrylonitrile, chloroacrylonitrile, styrene, methylstyrenes whichare substituted in the nucleus, 4-methoxystyrene, vinylcyclohexane,acrylic acid methyl, ethyl, isopropyl, 2-ethylhexyl and phenyl ester andmethacrylic acid methyl, ethyl, isopropyl, 2-ethylhexyl and phenylester, vinyl acetate and vinyl propionate, acrylic acid 2,3-epoxypropylester and methacrylic acid 2,3-epoxypropyl ester, benzoic acid vinylester, 2-vinylpyridine, 4-vinylpyridine, vinylimidazole,vinylpyrrolidone, methyl vinyl ketone, ethyl vinyl ketone, ethyl vinylether, n-butyl vinyl ether and divinylbenzene and di-, tri- ortetra-acrylates and -methacrylates of polyhydric alkanols.

COMPOUNDS OF THE FORMULA IV

Malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipicacid, suberic acid, sebacic acid and dodecanedicarboxylic acid,1,3-cyclopentane-dicarboxylic acid, hexahydroisophthalic acid,hexahydroterephthalic acid, terephthalic acid, isophthalic acid,4,4'-dicarboxydiphenylethane, naphthalene-2,6-dicarboxylic acid,thiophene-2,5-dicarboxylic acid and pyridine-2,3-dicarboxylic acid andthe corresponding dichlorides and diesters according to the definition;trimellitic acid 1,2-anhydride-chloride(1,3-dioxo-benzo[c]-oxalane-5-carboxylic acid chloride), trimelliticanhydride and trimellitic acid and esters according to the definition;pyromellitic dianhydride, 3,3',4,4'-benzophenone-tetracarboxylic aciddianhydride, 2,3,3',4'-benzophenone-tetracarboxylic acid dianhydride,2,2',3,3'-benzophenone-tetracarboxylic acid dianhydride,3,3',4,4'-diphenyl-tetracarboxylic acid dianhydride,bis-(2,3-dicarboxyphenyl)-methane dianhydride,bis-(2,5,6-trifluoro-3,4-dicarboxyphenyl)-methane dianhydride,2,2-bis-(2,3-dicarboxyphenyl)propane dianhydride,bis-(3,4-dicarboxyphenyl) ether dianhydride,bis-(3,4-dicarboxyphenyl)-sulphone dianhydride,N,N-(3,4-dicarboxyphenyl)-N-methylamine dianhydride,bis-(3,4-dicarboxyphenyl)-diethylsilane dianhydride, 2,3,6,7- and1,2,5,6-naphthalene-tetracarboxylic acid dianhydride,2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride,thiophene-2,3,4,5-tetracarboxylic acid dianhydride,pyrazine-2,3,5,6-tetracarboxylic acid dianhydride andpyridine-2,3,5,6-tetracarboxylic acid dianhydride.

COMPOUNDS OF THE FORMULA V

(diamines, diols and aminoalcohols) o-, m- and p-phenylenediamine,diaminotoluenes such as 2,4-diaminotoluene,1,4-diamino-2-methoxybenzene, 2,5-diaminoxylene,1,3-diamino-4-chlorobenzene, 4,4'-diaminodiphenylmethane,4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl thioether,4,4'-diaminodiphenylsulphone, 2,2'-diaminobenzophenone,4,4'-diaminodiphenylurea, 1,8- or 1,5-diaminonaphthalene,2,6-diaminopyridine, 1,4-piperazine, 2,4-diaminopyrimidine,2,4-diamino-s-triazine, di-, tri-, tetra-, hexa-, hepta-, octa- anddeca-methylenediamine, 2,2-dimethylpropylenediamine,2,5-dimethylhexamethylenediamine, 4,4-dimethylheptamethylenediamine,3-methylheptamethylenediamine, 3-methoxyhexamethyldiamine,2,11-diaminododecane, 2,2,4- and 2,4,4-trimethylhexamethylenediamine,1,2-bis-(3-aminopropoxy)-ethane, N,N'-dimethylethylenediamine,N,N'-dimethyl-1,6-diaminohexane and the diamines of the formulae H₂N(CH₂)₃ O(CH₂)₂ O(CH₂)₃ NH₂ and H₂ N(CH₂)₃ S(CH₂)₃ NH₂ ;1,4-diaminocyclohexane, 1,4-bis-(2-methyl-4-aminopentyl)-benzene and1,4-bis-(aminomethyl)-benzene; ethylene glycol, propylene glycol,1,3-propanediol, 1,4-, 1,3- and 2,3-butanediol,2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,5- and2,4-pentanediol, 1,6- and 2,5-hexanediol, 1,8-octanediol,1,12-dodecanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,10-decanediol,diethylene glycol, dipropylene glycol andN,N-bis-(2-hydroxyethyl)-ethylamine (N-ethyldiethanolamine);ethanolamine, 3-amino-1-propanol, 2-amino-1-butanol, 4-amino-1-butanol,5-amino-1-pentanol and 6-amino-1-hexanol; 1,2-, 1,3- and1,4-cyclohexanediol, 1,4-bis-(hydroxymethyl)-cyclohexane and4-amino-cyclohexanol; 1,2-, 1,3- and 1,4-dihydroxybenzene,1,2-dihydroxy-3-methoxybenzene, 1,2-dihydroxy-4-nitrobenzene,2,6-dihydroxytoluene, 1,3-, 1,4-, 1,5- and 1,6-dihydroxynaphthalene,2,2'-dihydroxybiphenyl, 4,4'-dihydroxy-biphenyl,4,4'-dihydroxy-diphenylmethane, 2,2'-bis-(4-hydroxyphenyl)-propane(bisphenol A), 2,2'- and 4,4'-dihydroxy-diphenyl ether and 3,3'- and4,4'-dihydroxy-diphenylsulphone; 2,4-dihydroxy-5-methyl-pyrimidine,2,3-dihydroxypyridine and 3,6-dihydroxy-pyridazine.

Appropriately, anhydrides, acid anhydrides or ester-anhydrides accordingto the definition, and preferably compounds of the formula IIa, andespecially compounds of the formula Ia, wherein R₁ represents --OH or analkoxy group with 1-4 carbon atoms and the two R₂ s conjointly representthe --O-- grouping, are used for the polymerisation according to processvariant (a).

Advantageously, acid chloride-anhydrides or ester-anhydrides of theformula Ib or esters or anhydrides of the formula IIb, but veryparticularly compounds of the formula Ib wherein R₁ ' represents achlorine atom or an alkoxy group with 1-4 carbon atoms and the two R₂ 'sconjointly represent the --O-- grouping, are employed for thepolycondensation reactions according to process variant (b). Preferredcompounds of the formula IV are acid dichlorides, anhydride-chlorides ordianhydrides.

The homopolymerisation of the compounds of the formula Ia or IIa, ortheir copolymerisation with compounds of the formula III, can be carriedout in a manner which is in itself known, for example in the presence ofcustomary cationic or anionic initiators or in the presence of mixedcatalysts (Ziegler-Natta catalysts). Free-radical polymerisation ispreferred. In this case it is appropriate to use about 0.01 to 5% byweight, preferably 0.01 to 1.5% by weight, based on the total weight ofthe monomers, of free-radical initiators which are in themselves known,such as inorganic and organic peroxides or azo compounds, for examplehydrogen peroxide, potassium peroxydisulphate, tert.-butylhydroperoxide, di-tert.-butyl peroxide, peracetic acid, benzoylperoxide, diacyl peroxides, cumene hydroperoxide, tert.-butylperbenzoate, tert.-alkyl peroxycarbonates and α,α'-azo-isobutyronitrile.The reaction temperature for free-radical polymerisation is generallyabout 30°-100° C.

It is also possible to use redox systems, for example mixtures ofperoxides, such as hydrogen peroxide, and a reducing agent, such asdivalent iron ions, in the abovementioned concentrations forfree-radical polymerisation in the cold.

The polymerisation can be carried out in a homogeneous phase, forexample in bulk (block polymerisation) or in solution, or in aheterogeneous phase, that is to say as precipitation polymerisation,emulsion polymerisation or suspension polymerisation. Polymerisation insolution is preferred.

Examples of suitable solvents are water; optionally chlorinated aromatichydrocarbons, such as benzene, toluene, xylenes and chlorobenzene;chlorinated aliphatic hydrocarbons, such as methylene chloride,chloroform, tetrachloroethane and tetrachloroethylene; aliphatic andcycloaliphatic ketones, such as acetone, methyl ethyl ketone,cyclopentanone and cyclohexanone; cyclic ethers, such astetrahydrofurane, tetrahydropyrane and dioxane; cyclic amides, such asN-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone andN-methyl-ε-caprolactam; N,N-dialkylamides of aliphatic monocarboxylicacids with 1-3 carbon atoms in the acid part, such asN,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide andN,N-dimethyl-methoxyacetamide; alkyl esters of aliphatic monocarboxylicacids with a total of 2-6 carbon atoms, such as formic acid methyl,ethyl and n-butyl ester or acetic acid methyl, ethyl and n-butyl ester;hexamethylphosphoric acid triamide (hexametapol);N,N,N',N'-tetramethylurea, tetrahydrothiophene dioxide (sulpholane) anddialkylsulphoxides, such as dimethylsulphoxide and diethylsulphoxide.

Mixtures of such solvents can also be used.

Preferred solvents are water, benzene, toluene, N,N-dimethylformamide,N,N-dimethylacetamide, ethyl acetate, tetrahydrofurane, chloroform andmethyl ethyl ketone as well as mixtures thereof.

The polycondensation of compounds of the formula Ib or IIb withcompounds of the formula V and, optionally, one or more compounds of theformula IV is also carried out in a manner which is in itself known,appropriately at temperatures of about -50° C. to +300° C. The reactioncan be carried out in the melt or, preferably, in an inert organicsolvent or a solvent mixture, optionally with the addition of knownpolymerisation inhibitors, such as hydroquinones, pyrocatechol orcresols, for example di-tert.-butylcresol. Temperatures of -20° C. to+50° C. are preferred for the polycondensation in solution.

Organic solvents which can be employed are those mentioned above.Preferred solvents for the reaction with diamines or amino-alcohols ofthe formula V are N,N-dialkylamides of aliphatic monocarboxylic acidswith 1-3 carbon atoms in the acid part, especiallyN,N-dimethylacetamide, and cyclic amides, such as N-methyl-pyrrolidone.

For the reaction with diols of the formula V, chlorinated aromatic oraliphatic hydrocarbons, such as chlorobenzene, methylene chloride,chloroform, tetrachloroethane and tetrachloroethylene, orN,N-dialkylamides of aliphatic monocarboxylic acids with 1-3 carbonatoms in the acid part, and especially chloroform orN,N-dimethylacetamide, are preferably employed.

The polycondensation of compounds of the formula Ib or IIb with diols ofthe formula V and, optionally, one or more compounds of the formula IVcan also be carried out in the melt, in the presence of customarypolycondensation catalysts, at temperatures of about 50° to 275° C. andunder a blanketing gas, such as nitrogen. Examples of catalysts whichcan be used are antimony compounds, such as antimony triacetate andantimony trioxide; zinc acetate, calcium acetate and germaniumcompounds.

The hydrochloric acid obtained during the polycondensation of compoundsof the formula Ib, wherein R₁ '=chlorine, with compounds of the formulaV and, optionally, one or more compounds of the formula IV can beremoved by neutralisation with basic substances, such as calciumhydroxide and triethylamine, or by reaction with an epoxy compound, suchas ethylene oxide or propylene oxide, and by washing out with suitablesolvents, for example water.

Polyamide-acid polymers or polyamide-amide-acid polymers obtainedaccording to the invention can, if desired, be cyclised, prior tocrosslinking, in a known manner, chemically or by the action of heat,for example by gentle treatment with a dehydrating agent on its own ormixed with a tertiary amine. Reagents which can be used are, forexample, acetic anhydride, propionic anhydride anddicyclohexylcarbodiimide or mixtures of acetic anhydride andtriethylamine. In order to prevent premature crosslinking, the reactionshould be carried out at tempratures which are as low as possible,preferably at a temperature below 50° C. and especially between about-20° C. and +20° C.

Crosslinking of the polymers according to the invention is effected in amanner which is in itself known, for example by the action of heat, byheating to temperatures of about 50° to 350° C., or chemically. Polymerswhich are obtained by polymerisation of compounds of the formula Ia orIIa with compounds of the formula III can be crosslinked, for example,in the presence of diamines, diols or amino-alcohols, for example thoseof the abovementioned formula V

    HY--Q--XH.

Crosslinking is usually carried out at temperatures of up to about 250°C.

Polycondensation products which are obtained by reacting compounds ofthe formula Ib or IIb and compounds of the formula IV with compounds ofthe formula V can be crosslinked in the presence of vinyl compounds, forexample those of the abovementioned formula III ##STR18## and optionallyin the presence of free-radical initiators, at temperatures betweenabout 50° and 200° C.

Finally, the polycondensation products according to the invention canalso be crosslinked by the action of light.

According to the process of the invention, polymers which have anydesired number, and statistical distribution, of the crosslinkablegroups can be manufactured and converted into polymers which have adegree of crosslinking suited to the particular application.

The polymers according to the invention, and especially those which areobtained using 5-50 mol % of a compound of the formula Ia, Ib, IIa orIIb, are distinguished by good processability and especially by goodsolubility in the customary organic solvents, such asN,N-dimethylformamide, N,N-dimethylacetamide, chloroform andtetrachloroethane, and also by improved flow properties in the melt.

They are suitable for the manufacture, in a manner which is in itselfknown and, if desired, using customary additives, such as pigments,fillers and the like, of industrial products, such as shaped articles ofvery diverse types, for example fibres, thin and thick films, coatingcompositions, lacquers, foams, adhesives, laminating resins, laminates,moulding powders, compression mouldings and the like. The productsobtained after crosslinking are resistant to solvents and display goodmechanical, electrical and/or thermal properties.

EXAMPLE 1

7.931 g (0.040 mol) of 4,4'-diaminodiphenylmethane are dissolved in 160ml of anhydrous N,N-dimethylacetamide (DMA) under a nitrogen atmosphere,in a sulphonation flask. This solution is cooled to -15° C. to -20° C. Amixture of 6.738 g (0.032 mol) of trimellitic anhydride-chloride and2.445 g (0.008 mol) of 5-maleimidyl-trimellitic anhydride-chloride inthe solid form is then added in portions, whilst stirring, at such arate that the temperature does not exceed -15° C. When the addition iscomplete, the solution is stirred for a further 1 hour at 20°-25° C.

Part of the resulting polymer solution is cast onto an aluminium foiland heated as follows: 30 minutes each at 70° C./20 mm Hg, 90° C./20 mmHg, 110° C./20 mm Hg, 130° C./20 mm Hg and 150° C./20 mm Hg, 1 hour at180° C./10⁻¹ mm Hg and 1 hour at 200° C./10⁻¹ mm Hg. A clear,mechanically strong coating of the crosslinked polyamide-imide isobtained. A transparent flexible film of good mechanical strength isobtained by dissolving off the aluminium foil with dilute hydrochloricacid.

EXAMPLE 2

3.056 g (0.01 mol) of 5-maleimidyl-trimellitic anhydride-chloride areintroduced in portions, whilst stirring and under a nitrogen atmosphereat -15° C., into a solution of 2.182 g (0.02 mol) of 3-aminophenol in 30ml of anhydrous DMA and the mixture is stirred for a further 30 minutes.2.030 g (0.01 mol) of isophthalic acid dichloride in the solid form arethen added at the same temperature, the reaction mixture is stirred for30 minutes and 3.033 g (0.03 mol) of triethylamine are then addeddropwise. The cooling bath is removed and the reaction mixture isstirred for 2 hours at 20°-25° C. The triethylamine hydrochloride whichhas precipitated is then filtered off. The resulting polymer solution iscast onto an aluminum foil and heated as described in Example 1. Atransparent coating of the cross-linked polyester-amide-imide isobtained.

EXAMPLE 3

Analogously to the procedure described in Example 1, 6.007 g (0.030 mol)of 4,4'-diaminodiphenyl ether are reacted with a mixture of 8.699 g(0.027 mol) of 3,3',4,4'-benzophenone-tetracarboxylic acid dianhydrideand 0.917 g (0.003 mol) of 5-maleimidyl-trimellitic anhydride-chloridein 150 ml of anhydrous DMA. The solution is processed by the methoddescribed in Example 1 to give films. Transparent, flexible films of thecrosslinked polyamide-imide, which have good mechanical strength, areobtained.

EXAMPLE 4

6.612 g (0.033 mol) of 1,12-diaminododecane are suspended in 140 ml ofanhydrous DMA under a nitrogen atmosphere in a sulphonation flask. Amixture of 8.699 g (0.027 mol) of 3,3',4,4'-benzophenone-tetracarboxylicacid dianhydride and 0.917 g (0.003 mol) of 5-maleimidyl-trimelliticanhydride-chloride in the solid form is added in portions to thissuspension, whilst stirring at -15° C. to -20° C. When the addition iscomplete, the reaction mixture is stirred for a further 30 minutes at 0°C. and then diluted with 110 ml of anhydrous DMA. The mixture is stirredfor a further 1 hour at 20°-30° C. and a further 1.93 g (0.006 mol) of3,3',4,4'-benzophenone-tetracarboxylic acid dianhydride in the solidform are then added at this temperature. After 30 minutes, the resultingpolymer solution is cast onto aluminum foils and heated as follows: 16hours at 80° C./20 mm Hg, 1 hour at 110° C./20 mm Hg and 1 hour at 130°C./20 mm Hg and for 2 hours at 130°-250° C./10⁻¹ mm Hg.

The crosslinked polyamide-imide is obtained as a transparent flexiblefilm of good mechanical strength by dissolving off the aluminium foilwith dilute hydrochloric acid.

EXAMPLE 5

45.06 g (0.5 mol) of butanediol together with 1,000 ml of anhydrouschloroform are initially introduced into a sulphonation flask. Aftercooling the resulting emulsion to -20° C., 91.36 g (0.45 mol) ofisophthalic acid dichloride in the solid form are added in a singleportion, whilst stirring. 106.2 g (1.05 mols) of anhydrous triethylamineare then added and the reaction mixture is stirred for 15 minutes at-20° C. During this time the reactants dissolve completely. 15.28 g(0.05 mol) of 5-maleimidyl-trimellitic anhydride-chloride in the solidform are then added and the reaction mixture is stirred for 30 minutesat -20° C. and then warmed to 20°-25° C. for one hour. During this timethe maleimidyl derivative dissolves. After stirring for 24 hours at20°-25° C., the solvent is evaporated in vacuo and the solid residue iscomminuted and suspended in 2,000 ml of methanol. After stirring for 2hours, the suspension is filtered and the residue is washed with waterand filtered off. The resulting polymer is then dried at 40° C.

4 g of the resulting polyester, together with 16 g of styrene and 0.1 gof dibenzoyl peroxide, are melted, under nitrogen, in a glass ampoule.On warming to 80° C., whilst shaking, the polyester goes into solution.The ampoule is now kept at 80° C. for a period of 16 hours and at 100°C. for 8 hours. A yellow, flexible, insoluble moulding is formed.

Pressing the polyester obtained according to paragraph 1 in a sheetpress at 120° C. for 1 hour under a light contact pressure gives a soft,very flexible moulding.

EXAMPLE 6

157.6 g (0.5 mol) of 5-maleimidyl-trimellitic anhydride-ethyl ester, 157g (1.5 mols) of styrene and 0.315 g of α,α'-azo-isobutyronitrile,together with 1,250 ml of anhydrous methyl ethyl ketone, are initiallyintroduced into a stirred vessel. The air is completely removed from thereaction vessel by flushing with nitrogen. The reaction mixture isheated to 70° C., whereupon everything goes into solution. Afterstirring for 12 hours at this temperature, the polymerisation isdiscontinued. The resulting yellow viscous solution is concentrated toabout half its volume. The polymer is precipitated out of this solutionby adding the solution dropwise to 5 litres of anhydrous benzene. Thepolymer is filtered off, 2 litres of cyclohexane are added and themixture is stirred for one hour and filtered again. The resulting paleyellow product is dried in vacuo at 100° C. Elementary analysis showsthat, after extracting by boiling in benzene, a copolymer in which themolar ratio of the starting monomers is about 1:1 has been formed.

4.0 g of the above copolymer are dissolved in 90 ml of ethyl methylketone and 0.54 g (0.005 mol) of m-aminophenol are added to thesolution. The solution is cast onto an aluminium sheet and dried for 30minutes at 50° C. and then for 16 hours at 150° C./100 mm Hg. A somewhatbrittle film is obtained and, in contrast to the copolymer which has notbeen crosslinked, this is insoluble in ethyl methyl ketone.

The imidyl compounds used in the above examples are prepared as follows:

5-Maleimidyl-trimellitic anhydride-chloride ##STR19##

96 g (0.5 mol) of trimellitic anhydride in 1,360 ml of H₂ SO₄ (97%strength) and 680 ml of 100% strength HNO₃ are heated at 97° C. for 19hours. The reaction solution is then poured onto 2,000 g of ice and themixture is stirred for 2 hours at -5° C. The 5-nitro-trimellitic acidwhich has crystallised out is dissolved in 125 ml of hot water and thesolution is rendered basic (pH 9) with 30% strength aqueous sodiumhydroxide solution and finally acidified to pH 1 with concentratedhydrochloric acid. The reaction solution is then evaporated to drynessand the residue is extracted with twice 400 ml of dioxane. The extractsare combined and evaporated to dryness, the residue is boiled with 120ml of benzene and the product is filtered off and dried. 66 g (51.7% oftheory) of 5-nitro-trimellitic acid are obtained.

102 g (0.4 mol) of this 5-nitro-trimellitic acid are hydrogenated at 30°C. in 1,000 ml of dioxane in the presence of 10 g of apalladium-on-charcoal catalyst containing 5% by weight of palladium. Thereaction solution is filtered and 46.8 g (0.48 mol) of maleic anhydrideare then added to the filtrate. The reaction mixture is left to stand atroom temperature (20°-25° C.) for 12 hours and then evaporated todryness at 60° C. in a rotary evaporator. The residue is twice heated tothe boil with, in each case, 400 ml of ethyl acetate, whilst stirring,and the product is then filtered off and dried for 24 hours at 80°C./100 mm Hg. 105 g (81.3% of theory) of 5-maleamidyl-trimellitic acidare obtained.

32.3 g (0.1 mol) of the 5-maleamidyl-trimellitic acid are mixed with 1.6g of anhydrous sodium acetate and 83 ml of acetic anhydride, and themixture is heated to 80° C. for 30 minutes. The resulting solution isevaporated to dryness and the residue is after-dried at 50° C./0.05 mmHg. 200 ml of thionyl chloride are added to the residue and the mixtureis heated to 80° C. for 2.5 hours. The reaction mixture is thenconcentrated to dryness, 150 ml of benzene are added to the residue, themixture is filtered and the filtrate is evaporated and, finally, theresidue is dried at 80° C./0.1 mm Hg. 50 ml of benzene are added to theresidue and the mixture is stirred intensively for 4 hours at 20°-25° C.A crystal slurry forms and the crystals are filtered off, then rinsedwith 20 ml of a 1:3 mixture by volume of cyclohexane and benzene andfinally dried for 12 hours at 80° C./0.1 mm Hg. 18.31 g (60% of theory)of crystalline 5-maleimidyltrimellitic anhydride-chloride are obtained;melting point 143°-144° C.

Analysis for C₁₃ H₁₄ NO₆ Cl (molecular weight 305.61): calculated C51.09%; H 1.32%; N 4.58%; found; C 51.09%; H 1.44%; N 4.57%.

5-Maleimidyl-trimellitic anhydride-ethyl ester

61.33 g (0.24 mol) of 5-nitro-trimellitic anhydride-chloride, obtainedby reacting 5-nitro-trimellitic anhydride with thionyl chloride, aredissolved in 120 ml of dioxane and 13.94 ml (0.24 mol) of ethanol areadded to the solution, whilst stirring. The reaction mixture is stirredat 25° C. for 12 hours, then heated to 80° C. for 1 hour and finallyevaporated to dryness. The residue is dissolved in 180 ml of dioxane and100 ml of water are added dropwise and after one hour the mixture isevaporated to dryness. The resulting residue is finely suspended in 100ml of benzene and the product is filtered off and dried at 80° C. in adrying cabinet. 60.5 g (89% of theory) of 5-nitro-trimellitic acid ethylester are obtained; melting point 189°-191° C.

65.13 g (0.23 mol) of 5-nitro-trimellitic acid ethyl ester are dissolvedin 150 ml of dioxane and hydrogenated at 30° C. in the presence of 6.5 gof a palladium-on-charcoal catalyst containing 5% by weight of Pd. Thereaction solution is filtered, 27 g of maleic anhydride are then addedto the filtrate and the mixture is left to stand for 12 hours at 20°-25°C. The solution is then evaporated at 40°-60° C. and 250 ml of diethylether are added to the oily residue, whilst stirring.5-Maleamidyl-trimellitic acid ethyl ester, which is deposited as a finewhite precipitate, is filtered off and dried at 50° C. in a dryingcabinet. 76.7 g (95% of theory) of the said ester are obtained; meltingpoint 142°-144° C.

58 g (0.165 mol) of the 5-maleamidyl-trimellitic acid ethyl ester areintroduced slowly, at 80° C., in the course of 15 minutes into a mixtureof 65 ml of acetic anhydride and 14.5 g of sodium acetate. The reactionmixture is stirred for 3 hours at this temperature and then concentratedto dryness and the residue is extracted with three times 200 ml oftoluene. The combined toluene extracts are evaporated to dryness,finally at 50° C./0.2 mm Hg. The solid residue is dissolved in 100 ml ofhot toluene and the solution is filtered. The 5-maleimidyl-trimelliticanhydride-ethyl ester which has crystallised out after the solution hascooled is filtered off and dried at 70° C. in a drying cabinet. 39.6 g(60% of theory) of 5-maleimidyl-trimellitic anhydride-ethyl ester whichhas a melting point of 178°-179° C. are obtained.

Analysis for C₁₅ H₉ NO₇ (molecular weight 315.24): calculated: C 57.14%;H 2.88%; N 4.44%; found: C 56.76%; H 3.03%; N 4.35%.

We claim:
 1. A crosslinkable polymer which has an average molecularweight of at least 1,200, or the corresponding cyclized imidederivative, which is manufactured by reacting at a temperature betweenabout -50° and 300° C. in the melt or in an inert organic solvent orsolvent mixture 0.5 to 100 mol% of a compound of the formula Ib or IIb##STR20## and 0 to 99.5 mol% of a compound of the formula IV ##STR21##with substantially stoichiometric amounts of a compound of the formula V

    HY--Q--XH

in which formulae m and n independently of one another represent thenumber 1 or 2, A represents a radical of the formula ##STR22## R₂ 'represents phenoxy; phenoxy substituted by one or two nitro groups, byone alkyl of 1 to 2 carbon atoms, by one alkoxy of 1 to 2 carbon atomsor by two to five halogen atoms; alkoxy with 1 to 18 carbon atoms or thetwo R₂ 's conjointly represent the --O-- grouping, R'₁ represents achlorine atom, phenoxy; phenoxy substituted by one or two nitro groups,by one alkyl of 1 to 2 carbon atoms, by one alkoxy of 1 to 2 carbonatoms or by two to five halogen atoms; or alkoxy of 1 to 18 carbonatoms, R₃ and R₄ independently of one another represent hydrogen,chlorine or bromine, X and Y represent --O-- or one of X and Yrepresents --O-- and the other denotes ##STR23## where R₅ representshydrogen, alkyl with 1-4 carbon atoms or phenyl, Q represents analiphatic radical with at least 2 carbon atoms or a cycloaliphatic,araliphatic, carbocyclic-aromatic or heterocyclic-aromatic radical, andQ₁ represents an aliphatic radical or a cycloaliphatic,carbocyclic-aromatic or heterocyclic-aromatic radical, in which thecarbonyl and carboxyl groups are bonded to different carbon atoms andthe carboxyl groups are each in the ortho-position relative to acarbonyl group, M₁ represents a chlorine atom, a hydroxyl group,phenoxy; phenoxy substituted by one or two nitro groups, by one alkyl of1 to 2 carbon atoms, by one alkoxy of 1 to 2 carbon atoms or by two tofive halogen atoms; or alkoxy with 1 to 18 carbon atoms, or when m or nis 2, M₁, conjointly with M₂, forms the --O-- grouping and the groups--COM₁ and --COM₂ are bonded to different carbon atoms and the --COM₁groups are each in the ortho-position relative to a --COM₂ group.
 2. Acrosslinkable polymer according to claim 1 which is manufactured byusing a compound of the formula Ib or IIb wherein A represents the group##STR24## or the --CH═CH-- group.
 3. A crosslinkable polymer which hasan average molecular weight of at least 1,200,which is manufactured byreacting at a temperature between about 30°-100° C. in bulk, solution,precipitation, emulsion or suspension polymerization in the presence of0.01 to 5% by weight based on the total weight of monomers, of afree-rdical initiator 0.5 to 100 mol % of a compound of the formula Iaor IIa ##STR25## with 0 to 99.5 mol % of a compound of the formula III##STR26## A represents a radical of the formula ##STR27## R₂ representshydroxyl, phenoxy; phenoxy substituted by one or two nitro groups, byone alkyl of 1 to 2 carbon atoms, by one alkoxy of 1 to 2 carbon atomsor by two to five halogen atoms; alkoxy with 1 to 18 carbon atoms or an--O--M⁺ group, or the two R₂ s conjointly represent the --O-- grouping,R₁ represents a hydroxyl group, phenoxy; phenoxy substituted by one ortwo nitro groups, by one alkyl of 1 to 2 carbon atoms, by one alkoxy of1 to 2 carbon atoms or by two to five halogen atoms; alkoxy of 1 to 18carbon atoms or --O--M⁺, with the proviso that when R₂ is hydroxyl, R₁cannot be --O--M⁺, and with the proviso that when R₂ is --O--M⁺, R₁cannot be hydroxyl, and M⁺ represents an alkali metal cation, atrialkylammonium cation with 3-24 carbon atoms or a quaternary ammoniumcation, R₃ and R₄ independently of one another represent hydrogen,chlorine or bromine, and Z₁ and Z₃ each represent hydrogen, Z₂represents hydrogen, chlorine or methyl and Z₄ represents hydrogen,methyl, ethyl, chlorine, --CN, --COOH, --CONH₂, phenyl, methylphenyl,methoxyphenyl, cyclohexyl, pyridyl, imidazolyl, pyrrolidonyl,--COO--alkyl with 1-12 carbon atoms in the alkyl part, --COO--phenyl,##STR28## --COO--alkyl--OH with 1-3 carbon atoms in the alkyl part or##STR29## wherein R₈ denotes a linear or branched saturated aliphaticradical with at most 10 carbon atoms, R₉ denotes hydrogen or methyl andx denotes an integer from 1 to 3; --OCO--alkyl with 1-4 carbon atoms inthe alkyl part, --OCO--phenyl, --CO--alkyl with 1-3 carbon atoms in thealkyl part, alkoxy with 1-6 carbon atoms, phenoxy, --CH═CH₂ or ##STR30##or Z₁ and Z₂ each represent hydrogen and Z₃ and Z₄ conjointly form the##STR31##
 4. Crosslinkable polymers according to claim 3, which ismanufactured by using 50-99 mol % of a compound of the formula III,wherein Z₁ and Z₃ each denote hydrogen, Z₂ denotes hydrogen or methyland Z₄ denotes --COO--alkyl with 1-10 carbon atoms in the alkyl part, orZ₁, Z₂ and Z₃ each denote hydrogen and Z₄ denotes --CN, chlorine, phenylor --OCOCH₃.
 5. A crosslinkable polymer according to claim 1, which ismanufactured by using 3-50 mol % of a compound of the formula Ib,wherein A represents the --CH═CH-- group, R₁ ' represents a chlorineatom or an alkoxy group with 1-4 carbon atoms and the two R₂ 'sconjointly represent the --O-- grouping.
 6. A crosslinkable polymeraccording to claim 1, which is manufactured by using a compound of theformula V and 50-97 mol % of a compound of the formula IV, in whichformulae one of X and Y denotes --O-- and the other denotes --NH--, Qdenotes the 1,3- or 1,4-phenylene group, m and n denote the number 1,the M₁ s each denote a chlorine atom and Q₁ denotes the 1,3- or1,4-phenylene group.
 7. A crosslinkable polymer according to claim 1,which is manufactured by using a compound of the formula V and 50-97 mol% of a compound of the formula IV, in which formulae X and Y each denote--O--, Q denotes an unsubstituted alkylene group with 2-12 carbon atoms,m and n denote the number 1, and M₁ s each denote a chlorine atom and Q₁denotes a 1,3- or 1,4-phenylene group.
 8. A crosslinkable polymeraccording to claim 1, which is manufactured by reacting about 50 mol %of 5-maleimidyltrimellitic anhydride-chloride and about 50 mol % ofisophthalic acid dichloride with 3-aminophenol.
 9. A crosslinkablepolymer according to claim 1 wherein A is --CH═CH--.
 10. A crosslinkablepolymer according to claim 3, which is manufactured by using 1-50 mol %of a compound of the formula Ia, wherein A represents the --CH═CH--group, R₁ represents --OH or an alkoxy group with 1-4 carbon atoms andthe two R₂ s conjointly represent the --O-- grouping.
 11. Acrosslinkable polymer according to claim 3 which is manufactured byusing a compound of formula Ia or IIa wherein A represents the group##STR32## or the --CH═CH-- group.
 12. A crosslinkable polymer accordingto claim 3 wherein A is --CH═CH--.
 13. A crosslinkable polymer accordingto claim 3 wherein the compound of formula Ia is5-maleimidyl-trimellitic anhydride ethyl ester and the compound offormula III is styrene.
 14. A crosslinkable polymer according to claim1, which is manufactured by reacting about 10 mol % of5-maleimidyltrimellitic anhydride-chloride and about 90 mol % ofisophthalic acid dichloride with butanediol.